The instant invention provides the compounds having the structures: ##STR2## which may also be defined according to the structure: ##STR3## wherein the wavy lines represent the "cis" or "trans" juxtaposition of the methyl, cyclohexenyl, hydrogen and carboxaldehyde moieties around the carbon-carbon double bond, and their uses thereof for their organoleptic properties in augmenting or enhancing the aromas and/or taste of consumable materials.
The materials which provide sweet, bready, lactonic aromas with milky, almond-like, cumin undertones are highly desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide sweet, fatty, nutty, buttery/lactone, coconut, aldehydic, lemon-like and orange aroma profiles and sweet, fatty, nutty, butter/lactone, coconut-like, aldehydic and orange-like taste profiles are highly desirable in the art of flavoring for foodstuffs, chewing gums, toothpastes, medicinal products and chewing tobaccos. Many of the natural materials which provide such flavor notes and contribute such desired nuances to flavorant compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace, enhance or augment the essential flavor and fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined coconut-like flavor, for example, has been difficult and relatively costly in the areas of both natural products and synthetic products.
Artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality and type and treatment of raw materials. Such variations can be reflected in the end products and result in unfavorable flavor charcteristics in said end products. Additionally the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies, dairy desserts and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavoring agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods, medicinal products, chewing gums and toothpastes is not completely known. This is particularly noticeable in products having coconut-like or fruity (citrusy) flavor characteristics.
Even more desirable are products which can serve as substitutes for difficult to obtain and natural perfumery oils and, at the same time, substitute for natural flavoring ingredients in foodstuffs, chewing gums, medicinal products and toothpastes and chewing tobaccos.
The compounds defined according to the structure: ##STR4## wherein the wavy lines represent the "cis" or "trans" juxtaposition of the methyl, cyclohexenyl, hydrogen and carboxaldehyde moieties around the carbon-carbon double bond, are indicated to be produced according to the paper by Dauphin, Kim Communications, October 1979, pages 799-801 (title: "Vilsmeier Formylation of Limonene A New Method For The Synthesis of Alfa-Atlantone") according to the reaction: ##STR5## wherein the compound having the structure: ##STR6## is produced in a ratio to the compound having the structure: ##STR7## of 40:1.
Cyclohexenyl acrolein derivative are known in the perfume and flavor arts for augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, perfumes and the like.
Thus, Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)" at Volume II, at monograph 2896 discloses the use of the compound having the structure: ##STR8## for augmenting or enhancing the aroma of perfumes. Arctander states:
"The subject material has found some application in perfumery, and so has the Cyclohexene carboxaldehyde from which it is made. The parent cyclic aldehyde has a powerful greenleafy odor, and it was interesting to see what type odor could be obtained by the Claisen condensation.
"Although rarely offered under its proper chemical name, this material is still used in various perfume specialties and bases for its refreshing, green note, sometimes useful in Citrus compositions, but also used in Chypres, Fougeres, etc. in a combination with Oakmoss, Lavender, etc.
"Prod.: from Acrolein and Butadiene to make Cyclohex-3-enealkehyde. By condensation (Claisen) with Acetaldehyde the title material is obtained. . . .
"The title aldehyde . . . was developed many years ago in a continuation of the search for interesting aldehydes from the Claisen reaction, by which Cinnamic aldehyde had been produced. It was also based upon a new method of obtaining Cyclohexene aldehydes and homologues of same."
Arctander, at monograph 2896, refers to the French Patent No. 672,025 published on Dec. 21, 1929 which discloses the Diels Alder reaction of a number of conjugated dienes with acrolein derivatives to produce cyclohexene carboxaldehydes according to, for example, the reaction: ##STR9## Said French Patent No. 672,025 further discloses at page 3, lines 79-82 and at page 4, lines 1-5, that aldehydes can be reacted with ketones such as acetone or methyl ethyl ketone to produce other compounds of the type "irone".
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I, at monographs 762 and 763, discloses the organoleptic uses of alpha-Cyclocitrylidene Acid Aldehyde (monograph 762) and beta-Cyclocitrylidene Acid Aldehyde (monograph 763) having the structures, respectively: ##STR10##
With respect to alpha-Cyclocitrylidene Acetaldehyde having the structure: ##STR11## Arctander states:
"Mild floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones.
"Suggested for use in perfume compositions. It bring a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. "Produced from alpha-Cyclocitral and Acetaldehyde by condensation."
As to beta-Cyclocitrylidene Acetaldehyde having the structure: ##STR12## Arctander states: "Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone.
"Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer.
"Produced from beta-Cyclocitral and Acetaldehyde by condensation."
Gamma cyclohexyl crotonaldehyde is disclosed to be useful in perfumery in U.S. Pat. No. 3,031,507 issued on Apr. 24, 1962. Gamma cyclohexyl crotonaldehyde has the structure: ##STR13##
Cinnamic aldehyde is well known in perfumery and substituted homologues thereof are known as intermediates for producing other useful compounds as shown by U.S. Pat. No. 3,313,843 disclosing compounds having the structure: ##STR14## wherein R can be alkyl or hydrogen, useful as intermediates in producing other compounds.
Nothing in the prior art however discloses the organoleptic utility of the compounds defined according to the structure: ##STR15## and nothing in the prior art indicates the unexpected, unobvious and advantageous uses of such compounds having the structure: ##STR16## wherein the wavy lines represent the "cis" or "trans" juxtaposition of the methyl, cyclohexenyl, hydrogen and carboxaldehyde moieties around the carbon-carbon double bond, for augmenting or enhancing the flavor and/or aroma of consumable materials including foodstuffs, chewing gums, medicinal products, toothpastes, perfumes, colognes and perfumed articles.